Production of gamma-sulfonyl carboxylic acids



Patented July 15, 1952 UNITED STATES PATENT a 1.603.658 i'P'RODUC'TIONTOF GAMMI AI-fstiLrioN'rL 1 i QWW? FritzHaniisch,..Ludwigshafen onethe fihine,

,Germany H No Drawing. Application March 17, 1951', Serial s eness113 91 1- i f scams. (01.2.60-515). V

their salts by reacting aliphatic gamma-lactones with salts of sulfinicacids.

Suitable initial materials are on the one hand, for example,gamma-butyrolactone and its alkyl, aryl or alkoxy substitution products,and on the other hand the sodium, calcium, zinc or potassium salts ofbenzene sulfinic acid or its homologues, halogen or alkoxy substitutionproducts, of methyl-, ethyl-, butyl-, decylor cycloalkylsulfinic acidsor mixtures of such sulfinic acids such as can be prepared for exampleby reducing the sulfochloride-like reaction products of chlorine andsulfur-dioxide on saturated hydrocarbons.

The reaction proceeds, for example when using gamma-butyrolactone andthe sodium salt of benzene sulflnic acid, according to the followingscheme:

CsHaSOr-CH1CHz-CHz-C ONE It is preferable to work so that the componentsact on each other for several hours, preferably while heating, forexample at 150 to 250 C. The co-employment of solvents or diluents isdesirable in many cases; for this purpose it is preferable to employ anexcess of the lactone. The use of increased pressure is generallyspeaking unnecessary.

The free gamma-sulfonyl carboxylic acids are obtained from the reactionmixture for example by dissolution in water and precipitation withmineral acids.

The compounds which are thus readily accessible according to the presentinvention are valuable intermediate products, for example for thedyestuff and pharmaceutical industries.

The following examples will further illustrate thisinvention but theinvention is not restricted to these examples. The parts are by weight.

Example 1 388 parts of the sodium salt of benzene sulfinic acid and 344parts of gamma-butyrolactone are heated at 180 to 200 C. for 4 to 6hours while stirring. The cooled solid mass is dissolved in water,acidified with hydrochloric acid and the resulting crystals filtered offby suction. 350 parts of gamma-benzenesulfonylbutyric acid are inExample 1.

obtained which after recrystallisation from ben zene melts at to 93 C.

Example 2 A sulfochloride mixture obtained by the action of chlorine andsulfurdioxide in short-wave light on a mixture of paraflin hydrocarbonshaving a boiling range of 250 to 320 C. is converted into a mixture ofsulfinic acids in the usual way with zinc dust and hydrochloric acid.parts of this sulfinic acid mixture is neutralised with 27 parts of 50%caustic soda solution. The water formed is distilled off under reducedpressure and 30 parts of gamma-butyrolactone are added to the salt-likeresidue.

The mixture is heated to 200 C. for 16 hours while stirring. The cooledmelt is dissolved in 200 parts of water, acidified with hydrochloricacid and the resulting mixture oi! gamma-alkylsulfonylbutyric acidsshaken up with benzene. After drying and distilling off the benzene,there remain 60 parts of an oil which is readily soluble in sodasolution and alcohol, which has an acid value of 143 and which has amean molecular weight of 390. It contains 65.08% of carbon. 10.75% ofhydrogen and 7.9% of sulfur.

What I claim is:

1. A process for the production of gamma-sulfonyl carboxylic acids whichconsists in reacting salts of sulfinic acids with aliphaticgamma-lactones.

2. A process for the production of gamma-arylsulfonyl carboxylic acidswhich consists in heating salts of aromatic sulflnic acids withgammabutyrolactones to'temperatures between and 250 C.

3. A process for the production of gammaphenyl-sulfonyl-butyric acidwhich consists in heating the sodium salt of benzene sulfinic acid withan excess of gamma-butyrolactone to temperatures between 180 and 200 C.and acidifying the reaction mixture after dissolving it in water.

4. A process for the production of gamma- (para-toluene-sulfonyl)-butyric acid which consists in heating the sodium salt'of para-toluenesulfinic acid with an excess of gamma-butyroalkyl-sulfonyl carboxylicacids which consists in heatingfsalts o f1 aliphatic su lflnicacidswith' gamma-butyrolactons to temheraturesi between 150 and250C.

. 6. A process for the production of a mixture ofgamma-alkyl-sulfonyl-butyric acids which consists in heating a mixtureof the sodium salts of 'sulfinic acids, obtained by reacting phrer e;"and sulfur-dioxide in short-wave light on a mix- "ture of paraflinhydrocarbons of a boiling' range 10 N umber 200 C. and acidifying thereaction mixture after dissolving it in water. Y FRITZ gmmiscn.

REFERENCES CITED The following referenc es. are, of ,r E 0rd in the fileof this patentz N t I FOREIGN PATENTS Country Date 676,013; Germany May26, 1939 Y E E 7 OTHER REFERENCES Johansson', Chem. Zentr., vol. 1916 IIp. 558. 7

between 250 and 320 C. and reducing the mix- 15 SchJanberg, Chem.Abstracts, ol. 37, C01. 5704 tur of sulfochlorides so obtained; by zinc;dust and hydrochloric acid, with an excessgof'gammav V butyrolactone totemperatures between 180 and I (19.43). Rapoportiet a1., Chem.Abstracts, V01."41, Col.

1. A PROCESS FOR THE PRODUCTION OF GAMMA-SULFONYL CARBOXYLIC ACIDS WHICHCONSISTS IN REACTING SALTS OF SULFINIC ACIDS WITH ALIPHATICGAMMA-LACTONES.